Kian Eisazadeh-Far Thermodynamic Properties of

Hameed Metghalchi
e-mail: metghalchi@coe.neu.edu
Ionized Gases at High
Mechanical and Industrial Engineering
Department,
Temperatures
Northeastern University, Thermodynamic properties of ionized gases at high temperatures have been calculated
Boston, MA 02115 by a new model based on local equilibrium conditions. Calculations have been done
for nitrogen, oxygen, air, argon, and helium. The temperature range is 300–100,000 K.
Thermodynamic properties include specific heat capacity, density, mole fraction of par-
James C. Keck ticles, and enthalpy. The model has been developed using statistical thermodynamics
Mechanical Engineering Department, methods. Results have been compared with other researchers and the agreement is good.
Massachusetts Institute of Technology, [DOI: 10.1115/1.4003881]
Cambridge, MA 02139
Keywords: thermodynamic properties, ionized gases, high temperature, plasma

1 Introduction pared with existing prior data and where the conditions overlap
the agreement is generally good.
The purpose of this paper is to provide the thermodynamic
properties of nitrogen, oxygen, air, argon, and helium at high tem-
peratures. These properties are needed for the study of spark dis- 2 General Model
charges where the electrical energy is deposited in a small kernel
The general model is based on statistical thermodynamic meth-
and converted to thermal energy in the gas. This is a high temper-
ods and it is assumed that the species are in thermodynamic equi-
ature process leading to the formation of plasmas with very high
librium. The physical constants of the ions and species are taken
degrees of ionization. The initial processes and the mechanisms of
from Fay [14] and Moore [15]. For nitrogen, oxygen, and air, the
plasma kernel formation are beyond the scope of this paper and
considered species are N2, N, Nþ, N2þ, N3þ, N4þ, N5þ, N6þ, O2,
more details can be found in other references [1–5]. However, as
O, Oþ, O2þ, O3þ, O4þ, O5þ, O6þ, O7þ, and e (electron). In addi-
the electrical energy is converted to the thermal energy, the tem-
tion to nitrogen, oxygen, and air plasma, the properties of two
perature of the plasma increases rapidly and the kernel grows. It is
inert gases, argon and helium, have been studied as well. The
to calculate this growth process that the thermodynamic properties
assumed species for argon are Ar, Arþ, Ar2þ, Ar3þ, Ar4þ, Ar5þ,
of the plasma, in particular, the specific heat capacity at constant
and Ar6þ and for helium are He, Heþ, and He2þ.
pressure, are needed.
We assume a diatomic gas at low temperatures. The number of
Prior calculations of the thermodynamic properties of high tem-
elemental atom number is then given by
perature plasmas have been carried out by several investigators
using a variety of models. Capitelli et al. [6] have calculated the X
z
thermodynamic properties of air at high temperature using empiri- EA ¼ 2A2 þ Ae e ¼ 0; 1; 2; 3; :::; z (1)
cal correlations. They calculated the specific heat capacity, den- e¼0
sity, molecular weight, thermal conductivity, viscosity, entropy,
enthalpy, and mole fraction of species over the temperature range where e is the charge number of the ions.
50,000 to 100,000 K. Giordano et al. [7] have calculated the ther- Total number of moles is given by
modynamic properties using statistical mechanical methods. Yos
[8] calculated the transport properties of air and its constituents in X
z
the temperature range 300–30,000 K. Sher et al. [9] studied the MA ¼ A2 þ e þ Ae (2)
birth of spark channels. For this purpose, they calculated the spe- e¼0
cific heat capacity and mole fractions of the air at high tempera-
tures using a simplified thermodynamic model but their results are Assuming charge neutrality, the mole number of free electrons is
not very accurate. Other studies performed in last few decades given by
include Behringer et al. [10], Jordan and Swift [11], Kopainsky X z
e¼ eAe (3)
[12], and Pateyron et al. [13]. Most of these calculations cover the e¼0
properties up to 50,000 K. However, for plasmas other than air,
such as the inert gases helium and argon, the available data in The equation of state is
temperature range up to 100,000 K is limited.
In this paper, we present a new model based on statistical pV ¼ MA RT (4)
mechanics which is both simple and accurate. Calculations have
been made for nitrogen, oxygen, air, argon, and helium. The tem- where p is the pressure, V is the volume, R is the universal gas
perature range is 300–100,000 K at constant atmospheric pressure. constant, and T is the temperature.
The calculated properties include specific heat capacity, density,
enthalpy, and the number of particles. Results have been com- 2.1 Dissociation. For a dissociation reaction,

A2 ! 2A þ DHd ; (5)
Contributed by the Advanced Energy Systems Division of ASME for publication
in the JOURNAL OF ENERGY RESOURCES TECHNOLOGY. Manuscript received April 26,
2010; final manuscript received February 25, 2011; published online May 26, 2011. DHd is the dissociation enthalpy. The equilibrium constant based
Assoc. Editor: Muhammad M. Rahman. on concentration is defined by

Journal of Energy Resources Technology Copyright V

C 2011 by ASME JUNE 2011, Vol. 133 / 022201-1

Downloaded From: https://energyresources.asmedigitalcollection.asme.org on 06/29/2019 Terms of Use: http://www.asme.org/about-asme/terms-of-use

 A2 2.2 Ionization Process. The governing equations for ioniza-
Ked ¼ (6) tion will now be described.
A2 V
For a typical ionization reaction
Using Eq. (4) to eliminate V in Eq. (6) we obtain
Ae1 ! Ae þ e þ DHe e ¼ 0; 1; 2; 3; :::; z (14)
2
A Ked RT Kpd
¼ ¼ (7) DHe is the ionization enthalpy. The equilibrium constant based on
A2 M p p
concentration is given by
At low temperature there are no ions (e  0), and Eqs. (1) and (2) Ae e
Kei ¼ e1 (15)
reduce to A V
A2 ¼ ðEA  AÞ=2 (8)
Using Eq. (4) to eliminate V in Eq. (15) we obtain
MA ¼ ðEA þ AÞ=2 (9) Ae e Kei RT Kpi
¼ ¼ (16)
Ae1 M p p
Substituting Eqs. (8) and (9) in Eq. (7) we will have
The number of elemental atoms involved in reaction (14) is
4Bd y2 ¼ 1  y2 (10)
EA ¼ Ae1 þ Ae (17)
where
y ¼ A=EA (10a) The total mole numbers is
Bd ¼ p=Kpd (10b)
MA ¼ EA þ e (18)
and Kpd is the equilibrium constant based on pressure.
Solving Eq. (10) we obtain The number of moles of electrons is

y0 ¼ ð1 þ 4Bd Þ1=2 (11) e ¼ ðe  1ÞAe1 þ eAe (19)

where X
z Combining Eqs. (17)–(19), we obtain
y0 ¼ ye (12)
e¼0 Ae1 ¼ EA  Ae (20)

From Eqs. (8) and (9) MA ¼ eEA þ Ae (21)

A 2 1  y0
y2 ¼ ¼ (13)
EA 2 e ¼ ðe  1ÞEA þ Ae (22)

Figure 1 shows the variation of y0, y2, and MA=EA for nitrogen Substituting Eqs. (20)–(22) in Eq. (16) then gives
dissociation. The normalized number of moles MA =EA, increases
due to dissociation of the molecule to atoms. The concentration of e
ðye Þ2 þ ðe  1Þye  ¼0 (23)
y must decrease at higher temperatures due to ionization. In the 1 þ Be
Sec. Ionization process, ionization process will be described to
complete the predictions. Solving this second-order equation, we find

Fig. 1 The variation of y0, y2, and MA=EA versus temperature Fig. 2 Variation of y0e , y0eþ1 , y e versus temperature during the
during the dissociation process ionization process

022201-2 / Vol. 133, JUNE 2011 Transactions of the ASME

Downloaded From: https://energyresources.asmedigitalcollection.asme.org on 06/29/2019 Terms of Use: http://www.asme.org/about-asme/terms-of-use

 Fig. 4 Mole fractions of oxygen species versus temperature
(“e” represents the electron)

progress of each reaction requires additional energy. Therefore, it

can be assumed that ionization is a step by step process and the
level of ionization increases with temperature.
Figure 3 shows the sketch of this model. The calculations are
performed in parallel and the individual packages are in mutual
equilibrium. The starting point is the bottom package (A2 $ 2A).
The normalized mole fraction of A versus elemental number of
nitrogen atoms is entered to the next package and the calculations
proceed; in the next package, the output will be Aþ and the same
pattern flows to the next ones. In each package, thermodynamic
equilibrium calculations are performed and the concentration of
each species is computed. The mole fractions of species are nor-
malized by the elemental number of atoms to ensure the conserva-
tion of mass. Given the temperature, pressure, and composition all
the thermodynamic properties of the plasma can be calculated.
The enthalpy is defined as
X
z
HA ¼ hA2 ðTÞA2 þ he ðTÞAe (27)
e¼0

Fig. 3 The sketch of equilibrium packages

( 1=2 )
1 4e
ye0 ¼ ðe  1Þ2 þ ðe  1Þ (24)
2 1 þ Be

ye0 ¼ ye þ yeþ1 þ    þ yz (25)

ye ¼ ye0  y0eþ1 (26)

It can be seen in Eq. (25) that ye0 involves the potential concentra-
tion of other ions in upper levels; so it increases and eventually
reaches unity. The actual concentration of ye is achieved by cor-
recting ye0 in Eq. (26) by taking into account the effect of next ion-
ization. Figure 2 shows the variations of ye , ye0 and y0eþ1 versus
temperature during the ionization process. The physical basis of Fig. 5 Mole fractions of nitrogen species versus temperature
this model is that ionization is an endothermic process and the (“e” represents the electron)

Journal of Energy Resources Technology JUNE 2011, Vol. 133 / 022201-3

Downloaded From: https://energyresources.asmedigitalcollection.asme.org on 06/29/2019 Terms of Use: http://www.asme.org/about-asme/terms-of-use

 Fig. 6 Mole fractions of argon plasma versus temperature (“e”
represents the electron) Fig. 8 Mole fractions of air species versus temperature
e
where hA2 ðTÞ is the enthalpy of molecule A2, and h (T) is the en- form the system of packages. This flexibility permits a wide range
thalpy for species Ae. of conditions to be covered by just one generic set of equations.
Normalized enthalpy will be For example, the model can treat the system of oxygen plasma,
Xz nitrogen plasma, and air plasma simultaneously.
HA
¼ hA2 ðTÞy2 þ heA ðTÞye (28)
EA e¼0
3 Results and Discussion
Heat capacity of the mixture is defined by Figures 4 and 5 show the mole fractions of oxygen and nitrogen
  z   plasma up to 100,000 K. The mole fractions in these two figures
cpA @HA =EA @hA @y2 X @heA e @ye are defined by
¼ ¼ y2 þ hA þ y þ heA
EA @T p @T @T e¼0
@T @T
  
(29) Ae MA
xA e ¼ for monatomic species and
EA EA
cp is the combination of translational, rotational, vibrational, and    (31)
electronics energy modes. It is defined by A2 MA
xA 2 ¼ for molecule
EA EA
cp ¼ ðcp Þtranslational þ ðcp Þrotational þ ðcp Þvibrational þ ðcp Þelectronics
(30) It can be seen that for both atoms, one dissociation and five ion-
izations (N5þ and O5þ) occur. The onset of ionization occurs
An important feature of this model is that the properties of the around 6000 K, and as the ionization proceeds, the mole fraction
individual ion packages are first calculated and then coupled to of species decrease. This is due to the increasing mole fraction of

Fig. 7 Mole fractions of helium plasma versus temperature Fig. 9 Plasma particle numbers normalized by elemental atom
(“e” represents the electron) numbers

022201-4 / Vol. 133, JUNE 2011 Transactions of the ASME

Downloaded From: https://energyresources.asmedigitalcollection.asme.org on 06/29/2019 Terms of Use: http://www.asme.org/about-asme/terms-of-use

 Fig. 10 Heat capacities of oxygen, nitrogen, argon, and helium Fig. 11 enthalpies of different species versus temperature; (a)
versus temperature; (a) helium and argon, (b) air, oxygen, and argon and helium, (b) air, oxygen, and nitrogen
nitrogen

electrons. Figures 6 and 7 show the mole fractions of argon and

helium.
Figure 8 shows the mole fractions of air plasma. The peaks of
this figure correspond to those in Figs. 4 and 5.
Figure 9 shows normalized particle numbers of oxygen, nitro-
gen, air, argon, and helium versus temperature. The particle num-
bers have been normalized by the elemental number of atoms. It
can be seen that under constant pressure condition, the number of
particles increase dramatically. It shows the effect of ionization
and increasing number of electrons. It is seen that the level of ion-
ization determines the number of particles. Since in helium there
are just two electrons, the number of particles does not increase as
much as for other species.
Figure 10 shows specific heat capacities of oxygen, nitrogen,
air, argon, and helium versus temperature. The several peaks at
this figure represent the reactions and production of atoms and
ions, which increase the heat capacity of the system. For oxygen
and nitrogen molecules, the role of rotational and vibrational
energy modes on heat capacity is important at lower temperatures.
However, after dissociation, the only energy mode of each species
is translational and electronic and the increase in the heat capacity Fig. 12 Heat capacity of air versus temperature and compari-
is just due to the ionization and the change of species concentra- son with other researchers (300–5000 K); - - - - , Ref. 6; –   –,
tion as can be seen in Eq. (29). Ref. 9; , Ref. 16; ——, present study

Journal of Energy Resources Technology JUNE 2011, Vol. 133 / 022201-5

Downloaded From: https://energyresources.asmedigitalcollection.asme.org on 06/29/2019 Terms of Use: http://www.asme.org/about-asme/terms-of-use

 Acknowledgment
This research has been supported by the Office of Naval
Research (ONR) grant number N00010-09-1-0479. The authors
are thankful for the technical monitoring of Dr. Gabriel Roy.

Nomenclature
A¼ the number of atom A
cp ¼ specific heat capacity
e¼ mole number of electron
EA ¼ number of elemental atom A
h¼ specific enthalpy
H¼ total enthalpy
K¼ equilibrium constant
M¼ total number of moles
P¼ pressure
R¼ gas constant
T¼ temperature
V¼ volume
x¼ mole fraction
z¼ total charge of the element
Fig. 13 Heat capacity of air versus temperature and compari- x¼ mole fraction
son with other researchers (300–100,000 K); -  -  -, Ref. 6; - - - - ,
Ref. 9; ——, present study
Greek Letters
A comparison between Figs. 4–8 and Fig. 10 shows that the e ¼ charge
peak values of heat capacities correspond to the stage where the
rate of dissociation and ionization is maximum. For example for Superscripts
air, first two peaks represent the equilibrium reaction of oxygen z ¼ total charge of the element
and nitrogen molecules and atoms and the rest of peaks corre- e ¼ charge of the species
spond to the ionization reactions. Since there are just two ioniza-
tion reactions in helium, consequently, only two peaks are Subscripts
observed in the figure. The behavior of this figure can be under- A¼ atom A
stood by the terms appeared in Eq. (29). d¼ dissociation
Figure 11 shows enthalpies of oxygen, nitrogen, air, argon, and e¼ equilibrium
helium versus temperature. At higher temperatures, the enthalpy d¼ dissociation
of helium exceeds the enthalpy of air. This is due to the higher p¼ constant pressure
heat capacity of helium at higher temperatures.
References
4 Comparison With Other Calculations [1] Bradley, D., Sheppard, C. G. W., Suardjaja, I. M., and Woolley, R., 2004,
Figure 12 shows values of specific heat and the comparison “Fundamentals of High-Energy Spark Ignition with Lasers,” Combust. Flame,
138(1–2), pp. 55–77.
with the results of Capitelli et al. [6], Sher et al. [9], and STAN- [2] El-Koramy, R. A., Effendiev, A. Z., and Aliverdiev, A. A., 2007, “The Pecu-
JAN equilibrium code [16] in temperature range of 300–5000 K. liarities of Spark Channel Formation in Air Gas at Atmospheric Pressure,”
Except for Sher et al., the agreement is good. In this range of tem- Physica B, 392(1–2), pp. 304–308.
perature, the concentration of ions is almost zero and the increase [3] Kravchik, T., and Sher, E., 1994, “Numerical Modeling of Spark Ignition and
Flame Initiation in a Quiescent Methane-Air Mixture,” Combust. Flame,
in heat capacity is due to the excitement of the vibrational energy 99(3–4), pp. 635–643.
modes and dissociation of oxygen atom. [4] Maly, R., 1981, “Ignition Model for Spark Discharges and the Early Phase of
Figure 13 compares the heat capacities of air calculated in Flame Front Growth,” Sym. (Int.) Combust., 18(1), pp. 1747–1754.
this study with those of Capitelli and Sher over the tempera- [5] Schäfer, M., Schmidt, R., and Köhler, J., 1996, “I-D Simulation of a Spark
Discharge in Air,” Sym. (Int.) Combust., 26(2), pp. 2701–2708.
ture range 300–100,000 K. This figure shows good agreement [6] Capitelli, M., Colonna, G., Gorse, C., and D’Angola, A., 2000, “Transport
with the results of Capitelli up to 70,000 K. Beyond 70,000 Properties of High Temperature Air in Local Thermodynamic Equilibrium,”
K, Capitelli et al. underestimates the heat capacity due to the Eur. Phys. J. D, 11, pp. 279–289.
neglect of the N5þ and O5þ ions in their study. Results of [7] Giordano, D., Capitelli, and M., Colonna, G., 1994, Tables of Internal
Partition Functions and Thermodynamic Properties of High-Temperature Air
Sher are limited to low temperatures that are in poor agree- Species From 50 K to 100000 K, European Space Agency (ESA), Paris, 237.
ment with the others. [8] Yos, J. M., 1963, “Transport Properties of Nitrogen, Hydrogen, Oxygen, and
Air to 30,000 Degrees K,” Avco Corp., Tech. Memo. RAD-TM-63-7, pp. 71.
5 Conclusions [9] Sher, E., Ben-Ya’Ish, J., and Kravchik, T., 1992, “On the Birth of Spark
Channels,” Combust. Flame, 89(2), pp. 214–220.
Thermodynamic properties of air, argon, and helium have [10] Behringer, K., Kollmar, W., and Mentel, J., 1968, “Messung der Wärmeleitfähig-
been calculated at high temperatures using a novel cascade ther- keit von Wasserstoff Zwischen 2000 und 7000  K,” Z. Phys. 215, pp. 127–151.
[11] Jordan, D., and Swift, J. D., 1973, “Measurement of Thermal Conductivity of
modynamic model. It was assumed that all species are in local Argon-Nitrogen Gas Mixtures at High Temperatures,” Int. J. Electron.,” 35(5),
thermodynamic equilibrium. The model is based on statistical pp. 595–608.
thermodynamics methods. [12] Kopainsky, J., 1971, “Strahlungstransportmechanismus und Transportkoeffi-
The calculated properties are specific heat capacity, enthalpy of zienten im Ar-Hochdruckbogen,” Z. Phys, 248(5), pp. 417–432.
[13] Pateyron, B., Elchinger, M. F., Delluc, G., and Fauchais, P., 1992,
the mixture, mole fraction of species, particle numbers, and den- “Thermodynamic and Transport Properties of Ar–H2 and Ar–He Plasma
sity. It is shown that all these properties are very temperature sen- Gases Used for Spraying at Atmospheric Pressure,” Plasma Chem. Plasma
sitive. It is also shown that number of ions and ionization level Process., 12(4), pp. 421–448.
play an important role in determining specific heat capacities and [14] Fay, J., 1965, Molecular Thermodynamics, Allison-Wesley, Reading, MA.
[15] Moore, C. E., 1971, “Atomic Energy Levels,” U.S. Department of Commerce,
particle numbers in the mixture. Results are compared with those National Bureau of Standards, NSRDS-NBS 35, Vol. 1.
of other researchers and good agreement is obtained in regions [16] Reynolds, W. C., 1980, STANJAN Interactive Computer Programs for Chemi-
where the results overlap. cal Equilibrium Analysis, Stanford University

022201-6 / Vol. 133, JUNE 2011 Transactions of the ASME

Downloaded From: https://energyresources.asmedigitalcollection.asme.org on 06/29/2019 Terms of Use: http://www.asme.org/about-asme/terms-of-use